Azo dyes adapted for dyeing regenerated cellulose materials



RAINALD isnierrrmm,

Patented Aug. 23, .1932

N T TATES] PATENT? mu le or, BLACKLEY, MANCHESTER,

ENGLAND; ASSIGNQB TO m- ]?EBIAL CHEMICAL INDUSTRIES LIMITED, OF WESI'MINSTEB, ENGLAND Azo DYES ineman FOR nirnnve REGENERATEDUCELLULOSE imms No Drawing, Application filed February 1 9, 193i), Serial No. 429,809, and? in Great Bri tain February 25,. it

azo dy uifs which' are valuable for the dyeing of a regenerated cellulose rayon, as-

for instance", a viscose rayon, and-which'are obtained by; coupling p-nitroaniline" disazo dyes which are obtained from m-- nitroaniline or its molecular substituted de-I rivatives by similar means possess the like valuable property of dyeing a cellulose rayon in even shades. 7

By this invention such azo dyes are obtained by coupling meta-nitroaniline or' a nuclear substituted derivative" thereof with a phenol or naphthol or a sulphonic or car boxylic acid derivative thereof, or with; an N-substituted aminonaphthol acid, reducing the nitro azo dyestuif produced, diazotizing the resultant aminoazo compound and coupling with a coupling component, including an azo coupling compound. According there are obtained dyestuifs giving yellow or1red to violet or blue shades on viscose rayon." Alternatively we may for instance couple a meta-aminoacetanilide or its corresponding nuclear substituted" derivatives with the aforesaid coupling components, hydrolyze the acylamino azo compound thus obtained and diazotize and couple with acoupling component d'yestuff.

My new disazo dyes may be generically represented by the probable formula:

' RiN='N-'R,-.i"

RN=N wherein R represents a benzene residue, R represents a benzene or naphthalene residue,

R represents a coupled residue of an :azo

dyecoupling component, A represents a COOH or $0 11 group and B represents hydrogen, an amino or substituted amino group, and in which azo groups attached to British Patents'Nos. 329,014 and 333,239, I have described blue or violet 'dis= with specified" coupling components, reducing theobtained, diazotizing regenerated g p and sulphonic to the components used the resultant aminoazo R arein the; meta-position with respect to each otherh Within the above class oficompounds Some of these subgeneric classes are as'follows:

wherein R represents a' benzene or naphthere are many subgeneric classes.

thalene residue, R represents hydrogen, an 7 alkyl or alkoxy group, pled residue of an azo, ponent, A represents, a

R represents a coudye coupling com- COOH or;- -S.Q H B represents hydrogen or an amino or substituted amino group. In the following formulae the various -symbols used have the same definitions as" set forthv ante;

and the additional symbols are defined as follows: R represents a naphthalene ,nucleus and R represents hydrogen, aryl or acyl group.

..,15': is crifum e V N=N a om).

soul), 7 1

wherein R represents hydrogen, an aryl or aeylgroup. p

7 1 R5 v 9. Q l

- v;.0H V N=N-1|2:OH

:1I V Y Y A on N=NRz-OH r- A 'N=N Y X I SOaH wherein X represents hydrogen or an SO H 53: group.

ing examples,

a 6155' limited. The

coon

'to which, however,'it is not parts are by Weight:

until reduction is completewhen itis 1 neutral by theaddition' of hydrochloric {Cid and the dyestuff precipitated by common salt.

teredoif, dissolved inhot water, cooled and; diazotizedjwith 300 parts of 36% I and about 69; parts oisodium' di zo: tiz ation is complete When' the diazo snspene,

chloric acid dium carbonate.

3 tized, coupl ed with 138' Eobample 1 'known manner and thedisazo solution is run-into a solution of 160 parts. of sodium salicylate containing 400 parts'of sodium stirring until combina-' carbonate. After 7 tion is complete the coupling is heated up 1 and the'dyestu'fimeduced by the addition of a solution containing360rparts of sodium The mixture is'stirred,

madesulphide crystals.

ni-trite; The mixture is stirred until sion is run into a' solution of 337,1partsof sodium salt of 2phenylaminO @naphthbl-Yi slilphonic acid containin'gfiQO partsof so- The. oup -1 v.m nr

stained cold'and alkaline, and after stirring until combination is complete it is heatedup and thedyestufi salted out Withc0mmon a salt. It dyes viscoserayon'an orange red Ifin place of the sodium salt of.

' Q-phenylamino-5 -naplithol-7 sulphonic acid;

.there is added. asolution containing 315 parts of Q-phenylamino-S-naphthol-6-sulphonic acid there is obtained'a dyestufi'dyeshade.

ing viscose rayona brown shade of good fastness-toacids. v

' {Ema-mph 2 I. i i

v i 138 of meta-nitroaniline are idiazoparts of jsalicylic acid; and the a resultant azo dyestuffsis successively reduced and diazotized as gde fj scribedin Example 1; Thediazo suspension thus obtained is stirred v into a neutral solu tion of the vmonoazo dyestufiobtained by coupling 138 parts of diajzotized p-nit roa aniline; with 319 7 parts I of 1; 8-aminonaph.,

thol'-3:.6-disulphonic acid in acid solution'in the .known manner, to which 500' parts of sodium carbonate have added. I The mixture is alkaline and isstirred until coupling is com,-

, $llbsequentl Jben n ai d oid and plete, when the mixture is heated up andthe dyestufi isolated by the addition of common salt. It dyes viscose rayon a greenish blue shade of good fastness to acids. Example-'3 I 168 parts of 4-nitro-2-anisidine are diazotizedjin the knownmanner with 69 parts of sodium nitrite and 250parts of 36. hydrochloric acid. The diazo solution is run into. parts of -2phenylf-1, amino:8-naphthol-G-sulphonic acid and partsof -sodium carbonate; The mixture-is.

a; solutionconteiining .315

.m-nitroaniline N. W.-acid m-nitroaniline B-oxynaphthoic acid m-nitroaniline N. W.-acid maintained faintly alkaline and stirred until coupling is complete when it is heated up and there is run in a solution containing about 360 parts of sodium sulphide crystals. The mixture is stirred until reduction is complete when it is made neutral and the aminoazo dyestuif precipitated by the addition of common salt and filtered oil. The aminoazo dyestuff is dissolved in hot water, cooled anddiazotized with 300 parts of 36% hydrochloric acid and about 69 parts of so- Nitroazo dyestufls From 1:3-diamine and 2 phenylamino 8 naphthol 6 sulm-nitroaniline phonic acid (alkaline coupled).

2 phenylamino 5 naphthol 7 sulphonm-nitroaniline ic acid (alkaline coupled).

dyes VlS- mphenylene diamine 2-amino-8-naphthol-fi-sulphonic acid (acid coued). 1 :8-an1inonaphtl1ol-2 :4-disulphonic acid (alka-v 1:8-a1ninonaphthol-2:4-disulphonic acid (alka- 1-amino-8-naplithol-4-sulphonic acid (alkaline Benzoyl-Z 8amino-naphthbl-fi-sulphonic acid Benzoyl-2z5-amino naphth Benzoyl-2: 8-amino-napl1thol-fi-sulphonlc ac1d.. l:8-aminonaphthok3:fi-disulphonic acid Vl Znaphthol-G-sulphonic acid 1:8-aminonaphtl1ol-3:6-disulphonic acid 1-amino-5-naphtl1ol-7 -sulphonic acid im-nitroaniline i. Salicylic acid m-aminoacetanilide Salicylic acid m-mtroaniline l-naphtholA-sulphonic acid 4-n1tro-2-an1s1d1n 2-naphthol-7-sulphonic acid m-nitro Salicylic acid 4-nitro-o-toluidine- .i 2 phgnylamino 8- naphthol- 6 sulphonic aci m-nitroaniline Salicylic acid Having now particularly described and ascertained the nature of my said invention and in what manner the same is to be performed, I declare that what I claim is:

1. As new products, disazo dyes having in the form of the free acid the probable formula:

no p H the said disazo dyes being capable of dyeing regenerated cellulose in even level yellowishbrown shades.

2. As new products, disazo dyes having in the form of the free acid the probable formula:

coon

OH 0M0 the said disazo dyes being capable of dyeing regenerated cellulose in even level brown shades. Y r

3. As newproducts disazo dyes having in the form of the free acid the probable formula: p 7 y x 1 coon wherein It represents the coupled residue of an azo dye couplingcomponent of the class consisting of benzoyl-2: S-amino-naphthold-sulphonic acid and 2-phenylamino-8-naphthol-G-sulphonic acid, said disazo dyes being capable of dyeing regenerated cellulose in even level shades.

l. As new products disazo' dyes having in Shade on viscose Reduced, diazotized and coupled withrayon Yellowish-brown Red Bluish-red Reddish-violetQ Bluish-red line coupled).

line couple coupled) Orange Orange Bluish-red.

' olet Orange Brownish-violet ol-7-sulphonic acid Maroon the form of the free acid the probable formula SOzH

wherein R represents the coupled residue of an azo dye coupling component of the class consisting of salicylicv acid and meta-phenylene diamine, R represents hydrogen, methyl or methoxy group, and R represents a phenyl or benzoyl group, said disazo dyes being capable of dyeing regenerated cellulose in even level shades.

In testimony whereof I aflix my signature.

RAINALD BRIGHTMAN,

Certificate of Correction Patent No. 1,87 3,27 7 August 23, 1932.

RAINALD BRIGHTMAN It is hereby certified that error appears in the printed specification of the abovenumbered patent requiring correction as follows: Page 3, lines 107 to 114, claim 4, strike out the formula and insert instead:

and that the said Letters Patent should be read With this correction therein that the same may conform to the record of the case in the Patent Oflice.

Signed and sealed this 11th day of October, A. D. 1932.

[SEAL] M. J. MOORE,

Acting Oomvm'ssz'oner of Patents. 

